Fungicidal composition

ABSTRACT

A fungicidal composition is provided. The effective ingredients of the composition comprise active components A and B, wherein the active component A is a compound having a structure of Formula (I), and the active component B is mancozeb; and the weight ratio of the two components is 1:1-400. Also provided are a preparation method and use of the composition. Test results show that the fungicidal composition has an obvious synergistic effect, and more importantly, the application rate is reduced and the cost is lowered. The fungicidal composition is effective in controlling certain specific fungal diseases of the crops. Through the combination of different fungicides with different mechanisms and modes of action, the application rate of each single agent is effectively reduced, and a good effect on broadening the fungicidal spectrum, retarding the development of fungal resistance and improving the control effect is exhibited.

BACKGROUND Technical Field

The present invention relates to the field of protection of agriculturalplants, in particular to a fungicidal composition with improvedproperties, and particularly to a fungicidal composition comprising abenzisothiazolinone and mancozeb.

Related Art

Benzisothiazolinone compounds are a new broad-spectrum fungicide, whichis mainly used for controlling and treating various bacterial and fungaldiseases on cereal crops, vegetables, and fruits. The mechanisms offungicidal action mainly include destroying the nuclei structure of theharmful fungi to cause them to die due to lose of the core component,and interfering with the metabolism of the fungal cells to causephysiological disturbance, thus ultimately leading to death. When theagent is used in the early stage of disease development, the plants maybe effectively protected against infection of pathogens; and when theagent is used in an appropriately increased amount after the disease isdeveloped, the spread of the harmful fungi is considerably controlled,thus achieving dual actions of protection and eradication.

Mancozeb is a protective fungicide having high efficacy, low toxicity,low residue, and broad fungicidal spectrum, which is mainly used forcontrolling various fungal diseases on wheat, fruits, and vegetables.The mechanisms of fungicidal action is such that after application, alayer of breathable, water-permeable and light-transmissible denseprotective film is formed on the surface of leaves and fruits to inhibitthe germination and invasion of fungal spores and destroy the activityof various enzymes required for normal physiological metabolism offungi, thereby achieving the purpose of sterilization and diseaseprevention.

Practical experience in pesticides has shown that repeated and specificapplication of an active compound to control harmful fungi leads in manycases to the rapid selectivity of fungal strains. To reduce the risk ofselectivity of resistant fungal strains, a mixture of compounds withdifferent activities is generally used at present to control harmfulfungi. By combining active compounds with different mechanisms ofaction, it is possible to delay the development of resistance, reducethe application rate and reduce the cost.

SUMMARY

In view of the problems of resistance development and residue in thesoil encountered by fungicides in practical application, an object ofthe present invention is to screen out fungicides with differentmechanisms of bactericidal action, which are combined to obtain a newfungicidal composition, so as to enhance the control effect of thebactericides, delaying the resistance development, reduce the amount ofapplication, and reduce the cost.

Another object of the present invention is to provide a method forpreparing a fungicidal composition comprising active components A and Band use thereof in controlling the pests on crops in the agriculturalarea.

The objects of the present invention can be achieved through thefollowing measures.

A fungicidal composition having synergistic effect comprises activecomponents A and B, wherein the active component A is a compound havinga structure of Formula (I), and the active component B is mancozeb.

In Formula (I), R is selected from H or C₁-C₈ alkyl.

In the present invention, C₁-C₈ alkyl refers to a linear or branchedalkyl group having 1 to 8 carbon atoms, and includes C₁ alkyl (e.g.methyl), C₂ alkyl (e.g. ethyl), C₃ alkyl (e.g. n-propyl and i-propyl),C₄ alkyl (e.g. n-butyl, i-butyl, t-butyl, and s-butyl), C₅ alkyl (e.g.n-pentyl and the like), C₆ alkyl, C₇ alkyl, and C₈ alkyl, including, butnot limited to, C₁-C₆ alkyl, C₁-C₅ alkyl, and C₁-C₄ alkyl.

In a preferred embodiment, R is selected from H or C₁-C₄ alkyl.

In a further preferred embodiment, R is selected from H, —CH₃, or —C₄H₉.

In Formula (I), when R is H, A is 1,2-benzisothiazolin-3-one (BIT).

In Formula (I), when R is CH₃, A is 2-methyl-1,2-benzisothiazolin-3-one(MBIT).

In Formula (I), when R is C₄H₉, A is2-n-butyl-1,2-benzisothiazolin-3-one (BBIT), where in the formula, thebutyl is n-butyl.

The inventor has found through experiments that the composition of thepresent invention has an obvious synergistic effect on controllingbacterial or fungal diseases of crops and more importantly, theapplication rate is reduced and the cost is lowered. The compoundsconstituting the components A and B have different structures anddifferent mechanisms of action, and the combination of the two compoundscan broaden the fungicidal spectrum and retard the occurrence anddevelopment of fungal resistance to a certain extent. Moreover, no crossresistance exists between the components A and B.

The weight ratio between the two components in the fungicidalcomposition of the present invention is 1:3-300. In a preferredembodiment, the weight ratio between the active component A and theactive component B is 1:4-280. To make the synergistic effect betweenthe two components more obvious, the weight ratio between the componentsA and B may be further preferably 1:10-270.

In a preferred embodiment, the weight ratio between the components A andB may be adjusted to any one of 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10,1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, 1:100, 1:110, 1:120,1:130, 1:140, 1:150, 1:160, 1:170, 1:180, 1:190, 1:200, 1:210, 1:220,1:230, 1:250, 1:260, 1:270, 1:280, 1:290, and 1:300 at will, or beselected from a range delimited by any two ratios above.

The composition of the present invention may be prepared into apesticidally acceptable formulation with the active ingredients and apesticide aid or adjuvant.

In an embodiment, the content of the active components in thecomposition is 2-95%, and preferably 5-95% by weight.

In another embodiment, the composition is in the form of a pesticidallyacceptable formulation comprising 10-90 wt % of the active componentsand 90-10 wt % of a pesticide adjuvant.

The present invention provides use of the bactericidal compositioncomprising components A and B in the control of crop diseases in theagricultural area, in particular in the control of fungal or bacterialdiseases of certain crops.

The composition may specifically comprise a pesticide adjuvant, such asone or more of a carrier, a solvent, a dispersant, a wetting agent, abinder, a thickener, an adhesive, a surfactant, a fertilizer and thelike. A commonly used adjuvant may be blended during application.

The suitable adjuvant or aid may be a solid or liquid that is generallya material commonly used in the preparation of formulations, forexample, a natural or regenerated mineral substance, a solvent, adispersing agent, a wetting agent, an adhesive, a thickener, or abinder.

The composition of the present invention may be applied by administeringthe composition of the present invention to the aboveground parts ofplants, in particular to the leaves or leaf surface thereof. Thecomposition may be used for seed impregnation, or applied onto thesurface of the objects to be controlled. The application frequency anddosage depend on the pathogen biology and the climatic and maintenanceconditions. The locus where the plant is growing, for example ricefield, may be impregnated with a liquid formulation of the composition,or the composition is applied in solid form to the soil, for example, ingranular form (soil application), where the composition penetrates theplant through the roots via the soil (systemic action).

The composition of the present invention can be prepared into variouspesticidally acceptable formulations, including, but not limited to,emulsifiable concentrates, suspensions, wettable powders, waterdispersible granules, powders, granules, aqueous solutions, aqueousemulsions, microemulsions, bait, mother liquor, mother powder, and soon. In a preferred embodiment, the formulation in the present inventionis a wettable powder, a suspension, water dispersible granules, anaqueous emulsion or a microemulsion. Depending on the properties of thecompositions, the objectives intended to be achieved by applying thecompositions, and the environmental conditions, the compositions may beapplied by spraying, atomizing, dusting, scattering, or pouring.

The composition of the present invention may be prepared into variousformulations through known processes. The active ingredients may beuniformly mixed with an adjuvant such as a solvent or a solid carrierand a surfactant if needed, and ground to prepare a desired formulation.

The solvent may be selected from aromatic hydrocarbons containingpreferably 8 to 12 carbon atoms, for example, a xylene mixture,substituted benzene, or a phthalate ester, for example, dibutyl ordioctyl phthalate; aliphatic hydrocarbons, for example, cyclohexane orparaffin; alcohols, glycols and ethers and esters thereof, for example,ethanol, ethylene glycol, and ethylene glycol monomethyl ether; ketones,for example, cyclohexanone; high-polarity solvents, for example,N-methyl-2-pyrrolidone, dimethyl sulfoxide, or dimethyl formamide; andvegetable oils, for example, soy bean oil.

The solid carrier includes for example natural mineral fillers generallyused in powders and dispersible powders, for example, talc, kaolin,montmorillonite or activated bauxite. To manage the physical propertiesof the composition, highly dispersive silicic acid or highly dispersiveabsorbent polymer carrier may also be added, for example, granularadsorptive carrier or non-adsorptive carrier. The suitable granularadsorptive carrier is porous, for example, pumice, soapy clay orbentonite. The suitable non-adsorptive carrier includes for examplecalcite or sand. Moreover, a large amount of inorganic or organicmaterial that is pre-prepared into granules and especially dolomite maybe used as the carrier.

As desired by the chemical nature of the active ingredients in thecomposition according to the present invention, the suitable surfactantincludes lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, alkaline earth metal or amine salts, alkylarylsulfonates,alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andethylene glycol sulfated fatty alcohol ethers, condensation products ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensation products of naphthalene or naphthalenesulfonic acid withphenol and formaldehyde, polyoxyethylene octyl phenyl ethers,ethoxylated iso-octylphenol, octylphenol, nonylphenol, alkylarylpolyethylene glycol ethers, tributylphenyl polyethylene glycol ether,tristearylphenyl polyethylene glycol ether, alkylaryl polyetheralcohols, ethoxylated castor oil, polyoxyethylene alkyl ethers,condensation products of ethylene oxide, ethoxylated polyoxypropylene,polyethylene glycol ether laurate acetal, sorbates, waste lignin sulfiteliquor, and methyl cellulose.

When a liquid formulation is prepared, the active ingredient A may befirst dissolved in a basic material to form a metal salt ofbenzisothiazoline. Suitable basic materials include alkali metalcarbonates, alkali metal hydroxides (e.g. sodium and potassiumhydroxide), alkali metal alkoxycarbonates, alkali metal alkoxides ormagnesium methoxide.

The two active ingredients in the composition of the present inventionhave a synergistic effect, such that the activity of the composition isobviously higher than the respective activity or expected sum of therespective activity of single compounds alone. The synergistic effect ismanifested as reduced application rate, broadened fungicidal spectrum,fast onset of action, long-lasting control effect, better control ofharmful fungi on plants by only one or a few applications, and broadenedpossible application interval. These features are particularly needed inthe fungal control practice of plants.

The fungicidal composition of the present invention is applicable to thecontrol of crop diseases in the agricultural area, and the specificdiseases to be treated include, but are not limited to, peach bacterialshot hole, tobacco wildfire, rice sheath blight, cucumber angular leafspot, cucumber downy mildew, rice bacterial leaf streak, rice bacterialfoot rot, bacterial wilt of corn, Fusarium wilt of watermelon, downymildew of grape, tomato bacterial wilt, eggplant bacterial wilt, ricefalse smut, rice bacterial leaf streak, pepper anthracnose, litchiulcerates, grape anthracnose, tobacco bacterial wilt, cucumberanthracnose, celery leaf blotch, lotus root blight, strawberry powderymildew, lettuce downy mildew, celery gray mold, apricot bacterial shothole, peach ulcerates, onion downy mildew, cotton bacterial angular leafspot, cucumber bacterial leaf blight and the like.

The composition of the present invention exhibits the followingadditional features. 1. The composition of the present invention has anobvious synergistic effect. 2. Because the two individual agents in thecomposition of the present invention have highly different structuresand completely different mechanisms of action, no cross resistanceexists, such that the problem of resistance development occurred due tothe use of single agents alone can be retarded. 3. The composition ofthe present invention is safe for the crops and has good efficacy. Thetest proves that the fungicidal composition of the present invention hasstable chemical properties, significant synergistic effects and obvioussynergistic and complementary effects on the objects controlled.

DETAILED DESCRIPTION

To make the objects, the technical solution, and advantages of thepresent invention clearer, the present invention is described in furtherdetail with reference to examples. It should be understood that thespecific examples described herein are merely provided for illustrating,instead of limiting the present invention. Any modifications andequivalent improvements and substitutions can be made thereto withoutdeparting from the spirit and principle of the present invention, whichare all fall within the protection scope of the present invention.

The percentages given in all the formulations in the examples below areall weight percentages. The various formulations are processed from thecomposition of the present invention by a process known in the prior artwhich may be varied as desired.

I. PREPARATION EXAMPLES OF FORMULATIONS (I) Processing and Examples ofWater Dispersible Granules

The active components A and B, an adjuvant and a filler were mixedevenly according to the ratio of the formulation, comminuted by gasstream into a wettable powder, then added with an amount of water,mixed, extruded, granulated, dried, and sieved, to obtain a waterdispersible granule product.

1. Preparation of Water Dispersible Granules of Active Component A (BIT)and Active Component B Example 1: 71% BIT⋅Mancozeb Water DispersibleGranules

BIT 1%, mancozeb 70%, potassium dodecyl sulfonate 5%, ammonium sulfate3%, potassium alkyl naphthalene sulfonate 4%, and light calciumcarbonate q.s. to 100%.

Example 2: 50.5% BIT⋅Mancozeb Water Dispersible Granules

BIT 0.5%, mancozeb 50%, sodium methyl naphthalene sulfonate-formaldehydecondensate 5%, sodium dodecyl sulfate 3%, sodium ligninsulfonate 6%, anddiatomite q.s. to 100%.

Example 3: 25.1% BIT⋅Mancozeb Water Dispersible Granules

BIT 0.1%, mancozeb 25%, sodium carboxymethyl starch 2%, sodium dodecylsulfate 4%, Xantham gum 2%, sodium ligninsulfonate 6%, and attapulgiteq.s. to 100%.

2. Preparation of Water Dispersible Granules of Active Component A(MBIT) and Active Component B Example 4: 71% MBIT⋅Mancozeb WaterDispersible Granules

MBIT 1%, mancozeb 70%, with the remaining components being the same asthose in Example 1.

Example 5: 50.5% MBIT⋅Mancozeb Water Dispersible Granules

MBIT 0.5%, mancozeb 50%, with the remaining components being the same asthose in Example 2.

Example 6: 25.1% MBIT⋅Mancozeb Water Dispersible Granules

MBIT 0.1%, mancozeb 25%, with the remaining components being the same asthose in Example 3.

3. Preparation of Water Dispersible Granules of Active Component A(BBIT) and Active Component B Example 7: 71% BBIT⋅Mancozeb WaterDispersible Granules

BBIT 1%, mancozeb 70%, with the remaining components being the same asthose in Example 1.

Example 8: 50.5% BBIT⋅Mancozeb Water Dispersible Granules

BBIT 0.5%, mancozeb 50%, with the remaining components being the same asthose in Example 2.

Example 9: 25.1% BBIT⋅Mancozeb Water Dispersible Granules

BBIT 0.1%, mancozeb 25%, with the remaining components being the same asthose in Example 3.

(I) Processing and Examples of Suspensions

The active ingredients A and B were uniformly mixed with a dispersingagent, a wetting agent, a thickener, water and other components inproportion, and ground and/or high-speed sheared to give a semi-finishedproduct, which was analyzed, supplemented with water, mixed uniformly,and filtered, to obtain a finished product.

1. Preparation of Suspensions of Active Component A (BIT) and ActiveComponent B Example 10: 4% BIT⋅Mancozeb Suspension

BIT 1%, mancozeb 3%, Xanthan gum 3%, bentonite 4%, magnesium aluminumsilicate 2%, ethylene glycol 2%, sodium ligninsulfonate 7%, and waterq.s. to 100%.

Example 11: 15.1% BIT⋅Mancozeb Suspension

BIT 0.1%, mancozeb 15%, bentonite 4%, glycerol 3%, sodium methylnaphthalene sulfonate-formaldehyde condensate 5%, and water q.s. to100%.

Example 12: 21% BIT⋅Mancozeb Suspension

BIT 1%, mancozeb 20%, white carbon black 3%, glycerol 6%, sodiumbenzoate 2%, fatty alcohol polyoxyethylene ether phosphate 7%, and waterq.s. to 100%.

Example 13: 5% BIT⋅Mancozeb Suspension

BIT 1%, mancozeb 4%, white carbon black 4%, ethylene glycol 5%, sodiumligninsulfonate 7%, Xantham gum 2%, and water q.s. to 100%.

2. Preparation of Suspensions of Active Component A (MBIT) and ActiveComponent B Example 14: 4% MBIT⋅Mancozeb Suspension

MBIT 1%, mancozeb 3%, with the remaining components being the same asthose in Example 10.

Example 15: 15.1% MBIT⋅Mancozeb Suspension

MBIT 0.1%, mancozeb 15%, with the remaining components being the same asthose in Example 11.

Example 16: 21% MBIT⋅Mancozeb Suspension

MBIT 1%, mancozeb 20%, with the remaining components being the same asthose in Example 12.

Example 17: 5% MBIT⋅Mancozeb Suspension

MBIT 1%, mancozeb 4%, with the remaining components being the same asthose in Example 13.

3. Preparation of Suspensions of Active Component A (BBIT) and ActiveComponent B Example 18: 4% BBIT⋅Mancozeb Suspension

BBIT 1%, mancozeb 3%, with the remaining components being the same asthose in Example 10.

Example 19: 15.1% BBIT⋅Mancozeb Suspension

BBIT 0.1%, mancozeb 15%, with the remaining components being the same asthose in Example 11.

Example 20: 21% BBIT⋅Mancozeb Suspension

BBIT 1%, mancozeb 20%, with the remaining components being the same asthose in Example 12.

Example 21: 5% BBIT⋅Mancozeb Suspension

BBIT 1%, mancozeb 4%, with the remaining components being the same asthose in Example 13.

(III) Processing and Examples of Wettable Powder

The active ingredients A and B and various additives and fillers werefully mixed in proportion, and ground by an ultrafine grinder to preparea wettable powder.

1. Preparation of Wettable Powders of Active Component A (BIT) andActive Component B Example 22: 60.2% BIT⋅Mancozeb Wettable Powder(1:300)

BIT 0.2%, mancozeb 60%, sodium dodecyl benzene sulfonate 2%, calciumlignosulphonate 3%, bentonite 3%, and attapulgite q.s. to 100%.

Example 23: 40.2% BIT⋅Mancozeb Wettable Powder (1:200)

BIT 0.2%, mancozeb 40%, Nekal 2%, bentonite 1.5%, alkyl polyoxyethyleneether sulfonate 1%, white carbon black 2%, and diatomite q.s. to 100%.

Example 24: 51% BIT⋅Mancozeb Wettable Powder (1:50)

BIT1%, mancozeb 50%, sodium ligninsulfonate 6%, alkyl sulfonate 7%,white carbon black 10%, and Kaolin q.s. to 100%.

2. Preparation of Wettable Powders of Active Component A (MBIT) andActive Component B Example 25: 60.2% MBIT⋅Mancozeb Wettable Powder

MBIT0.2%, mancozeb 60%, with the remaining components being the same asthose in Example 22.

Example 26: 40.2% MBIT⋅Mancozeb Wettable Powder

MBIT0.2%, mancozeb 40%, with the remaining components being the same asthose in Example 23.

Example 27: 51% MBIT⋅Mancozeb Wettable Powder

MBIT1%, mancozeb 50%, with the remaining components being the same asthose in Example 24.

3. Preparation of Wettable Powders of Active Component A (BBIT) andActive Component B Example 28: 60.2% BBIT⋅Mancozeb Wettable Powder

BBIT 0.2%, mancozeb 60%, with the remaining components being the same asthose in Example 22.

Example 29: 40.2% BBIT⋅Mancozeb Wettable Powder

BBIT 0.2%, mancozeb 40%, with the remaining components being the same asthose in Example 23.

Example 30: 51% BBIT⋅Mancozeb Wettable Powder

BBIT 1%, mancozeb 50%, with the remaining components being the same asthose in Example 24.

II. EFFICIENCY VERIFICATION TEST (I) Bioassay Examples

Based on the test grade scale, the disease development on the leaves ofthe whole cucumber plant was investigated, and the disease index andcontrol effect were calculated.

The control effect was converted into probability (y), the concentrationof the agents (μg/ml) in solution was converted into a logarithmic value(x), the toxic regression equation and the median inhibitionconcentration EC50 were calculated by least square method, and thetoxicity index and the co-toxicity coefficient (CTC) of the agents werecalculated by SUN Peiyun method.

Actual toxicity index (ATI)=(EC50 of standard/EC50 of test agent)*100

Theoretical toxicity index (TTI)=toxicity index of agent A*percentagecontent of A in the mixture+toxicity index of agent B*percentage contentof B in the mixture

Co-toxicity coefficient (CTC)=[actual toxicity index (ATI) of themixture/theoretical toxicity index (TTI) of the mixture]*100

≥Where CTC≤80, the composition exhibits an antagonistic effect; where80<CTC<120, the composition exhibits an additive effect, and whereCTC≥120, the composition exhibits a synergistic effect.

1. Toxicity Test of BIT Combined with Mancozeb

TABLE 1 Toxicity test result analysis of BIT combined with mancozeb oncucumber downy mildew Co-toxicity EC₅₀ coefficient Name of agent (μg/ml)ATI TTI (CTC) BIT 13.5 100.00 / / Mancozeb 75.17 17.96 / / BIT:mancozeb= 1:300 60.79 22.21 18.233 121.81 BIT:mancozeb = 1:250 58.32 23.1518.287 126.58 BIT:mancozeb = 1:200 56.70 23.81 18.368 129.62BIT:mancozeb = 1:150 54.14 24.94 18.503 134.76 BIT:mancozeb = 1:10050.88 26.53 18.772 141.35 BIT:mancozeb = 1:75 50.41 26.78 18.233 146.87BIT:mancozeb = 1:50 48.29 27.95 19.569 142.85 BIT:mancozeb = 1:20 46.5628.99 21.867 132.59 BIT:mancozeb = 1:10 41.88 32.24 25.418 126.83BIT:mancozeb = 1:4 31.70 42.59 34.368 123.91 BIT:mancozeb = 1:3 29.0646.45 38.470 120.75 BIT:mancozeb = 1:2 25.70 52.52 45.307 115.93

The results (in Table 1) show that the control effect of the combinationof BIT and mancozeb on the cucumber downy mildew is significantlyimproved, suggesting that the combination of the two components has anobvious synergistic effect in the control of cucumber downy mildew.

2. Toxicity Test of MBIT Combined with Mancozeb

TABLE 2 Toxicity test result analysis of MBIT combined with mancozeb onpotato late blight Co-toxicity EC₅₀ coefficient Name of agent (μg/ml)ATI TTI (CTC) MBIT 14.81 100.00 / / Mancozeb 68.27 21.69 / /MBIT:mancozeb = 1:300 54.53 27.16 21.950 123.740 MBIT:mancozeb = 1:25051.61 28.69 22.002 130.414 MBIT:mancozeb = 1:200 50.28 29.45 22.080133.393 MBIT:mancozeb = 1:150 48.17 30.74 22.209 138.431 MBIT:mancozeb =1:100 45.50 32.55 22.465 144.889 MBIT:mancozeb = 1:75 45.50 32.55 21.950148.298 MBIT:mancozeb = 1:50 44.48 33.30 23.225 143.359 MBIT:mancozeb =1:20 42.75 34.65 25.419 136.304 MBIT:mancozeb = 1:10 39.34 37.64 28.809130.659 MBIT:mancozeb = 1:4 31.27 47.36 37.352 126.798 MBIT:mancozeb =1:3 29.25 50.64 41.268 122.701 MBIT:mancozeb = 1:2 26.04 56.86 47.793118.977

The results (in Table 2) show that the control effect of the combinationof MBIT and mancozeb on potato late blight is significantly improved,suggesting that the combination of the two components has an obvioussynergistic effect in the control of potato late blight. Particularlywhen the ratio of MBIT to mancozeb is in the range of 1:3-300, thesynergistic effect is obvious.

3. Toxicity Test of BBIT Combined with Mancozeb

TABLE 3 Toxicity test result analysis of BBIT combined with mancozeb onapple anthracnose Co-toxicity EC₅₀ coefficient Name of agent (μg/ml) ATITTI (CTC) BBIT 19.09 100 / / mancozeb 92.36 20.67 / / BBIT:mancozeb =1:300 75.22 25.38 20.934 121.237 BBIT:mancozeb = 1:250 72.22 26.4320.986 125.959 BBIT:mancozeb = 1:200 68.16 28.01 21.065 132.969BBIT:mancozeb = 1:150 65.71 29.05 21.195 137.058 BBIT:mancozeb = 1:10061.97 30.81 21.455 143.583 BBIT:mancozeb = 1:75 62.44 30.57 20.934146.048 BBIT:mancozeb = 1:50 60.89 31.35 22.225 141.068 BBIT:mancozeb =1:20 58.31 32.74 24.448 133.910 BBIT:mancozeb = 1:10 52.58 36.30 27.882130.207 BBIT:mancozeb = 1:4 41.36 46.15 36.536 126.316 BBIT:mancozeb =1:3 38.57 49.49 40.503 122.187 BBIT:mancozeb = 1:2 34.22 55.79 47.113118.415

The results (in Table 3) show that the control effect of the combinationof BBIT and mancozeb on apple anthracnose is significantly improved,suggesting that the combination of the two components has an obvioussynergistic effect in the control of apple anthracnose.

II. FIELD EFFICIENCY VERIFICATION TEST

Test method: in early stage of disease development, the first spray wasgiven immediately, and then the second application was given after 7days. Each treatment included 4 plots of 20 square meters each. Thedisease development before application and 11 days after the secondapplication was statistically investigated. Samples were collected from5 locations in each plot at random, and 5 plants were investigated ateach location by investigating the percentages of the disease spot areaon the leaves relative to the leaf area of the whole plant and grading.The disease index and the control effect were calculated.

${{Disease}\mspace{14mu} {index}} = {\frac{\Sigma ( {\begin{matrix}\begin{matrix}{{Number}\mspace{14mu} {of}\mspace{14mu} {leaves}\mspace{14mu} {at}} \\{{each}\mspace{14mu} {grade}\mspace{14mu} {of}\mspace{14mu} {disease}}\end{matrix} \\{development}\end{matrix} \times \begin{matrix}\begin{matrix}{{Representative}\mspace{14mu} {value}} \\{{of}\mspace{14mu} {corres}\text{-}}\end{matrix} \\{{ponding}\mspace{14mu} {grade}}\end{matrix}} )}{\begin{matrix}{{Total}\mspace{14mu} {number}\mspace{14mu} {of}} \\{{leaves}\mspace{14mu} {investigated}}\end{matrix} \times \begin{matrix}{Representative} \\{{value}\mspace{14mu} {of}\mspace{14mu} {highest}\mspace{14mu} {level}}\end{matrix}} \times 100}$${{Control}\mspace{14mu} {effect}\mspace{14mu} (\%)} = {( {1 - \frac{\begin{matrix}{{Disease}\mspace{14mu} {index}\mspace{14mu} {of}\mspace{14mu} {control}} \\{{group}\mspace{14mu} {before}\mspace{14mu} {application}}\end{matrix} \times \begin{matrix}{{Disease}\mspace{14mu} {index}\mspace{14mu} {of}\mspace{14mu} {treatment}} \\{{group}\mspace{14mu} {after}\mspace{14mu} {application}}\end{matrix}}{\begin{matrix}{{Disease}\mspace{14mu} {index}\mspace{14mu} {of}\mspace{14mu} {control}} \\{{group}\mspace{14mu} {after}\mspace{14mu} {application}}\end{matrix} \times \begin{matrix}{{Disease}\mspace{14mu} {index}\mspace{14mu} {of}\mspace{14mu} {treatment}} \\{{group}\mspace{14mu} {before}\mspace{14mu} {application}}\end{matrix}}} ) \times 100}$Anticipated control effect (%)=X+Y−XY/100

(where X and Y are the control effect of a single agent)

Grade Scale:

Grade 0: no disease spot;

Grade 1: number of disease spots on the leaf<5, and length<1 cm;

Grade 3: 6≤number of disease spots on the leaf≤10, and length of somedisease spots>1 cm;

Grade 5: 11≤number of disease spots on the leaf≤25, some disease spotsare contiguous, and the disease spot area is 10-25% of the leaf area;

Grade 7: number of disease spots on the leaf≥26, the disease spots arecontiguous, and the disease spot area is 26-50% of the leaf area;

Grade 9: the disease spots are contiguous, and the disease spot area isabove 50% of the leaf area, or all the leaves all wilted.

1. Field Efficacy Test of BIT Combined with Mancozeb

TABLE 4 Control effect of BIT combined with mancozeb on apple ring rotDay 11 after the second application Amount Disease index Disease ControlNo. Agent (mg/kg) before application index effect (%) Example 1 5% BITwater dispersible 16.9 11.94 18.19 25.36 granules 75% mancozeb water1183.1  9.74  8.93 55.08 dispersible granules Anticipated controlefficacy — — — 66.47 after mixing them 71% BIT • mancozeb 1200 10.53 5.37 75.04 water dispersible granules (BIT:mancozeb = 1:70) Example 23% BIT water dispersible 11.9 10.24 15.93 23.78 granules 75% mancozebwater 1188.1 11.76 10.27 57.23 dispersible granules Anticipated controlefficacy — — — 67.40 after mixing them 50.5% BIT • mancozeb 1200  9.02 4.56 75.26 water dispersible granules (BIT:mancozeb = 1:100) Example 33% BIT water dispersible 4.8 15.4  27.55 12.35 granules 75% mancozebwater 1195.2 10.56  8.42 60.94 dispersible granules Anticipated controlefficacy — — — 65.76 after mixing them 25.1% BIT • mancozeb 1200 13.03 7.65 71.23 suspension (BIT:mancozeb = 1:250) Example 10 5% BITsuspension 300 12.04  9.61 60.89 40% mancozeb suspension 900  9.94 15.4144.03 Anticipated control efficacy — — — 78.11 after mixing them 4% BIT• mancozeb 1200 10.56  5.15 84.12 suspension (BIT:mancozeb = 1:3)Example 11 5% BIT suspension 8 15.23 24.42 21.45 40% mancozeb suspension1192 10.47  8.87 58.51 Anticipated control efficacy — — — 67.41 aftermixing them 15.1% BIT • mancozeb 1200 11.21  6.01 73.75 suspension(BIT:mancozeb = 1:150) Example 12 5% BIT suspension 57.1 14.45 17.6640.12 40% mancozeb suspension 1142.9 12.74 14.51 44.2 Anticipatedcontrol efficacy — — — 66.59 after mixing them 21% BIT • mancozeb 120015.23  8.84 71.56 suspension (BIT:mancozeb = 1:20) Example 13 5% BITsuspension 240 10.45 11.04 48.23 40% mancozeb suspension 960 10.57 11.3647.35 Anticipated control efficacy — — — 72.74 after mixing them 5% BIT• mancozeb 1200  9.04  4.09 77.86 suspension (BIT:mancozeb = 1:4)Example 22 3% BIT wettable powder 4 12.45 22.81 10.24 80% mancozebwettable 1196 10    7.86 61.51 powder Anticipated control efficacy — — —65.45 after mixing them 60.2% BIT • mancozeb 1200 10.54  6.45 70.02wettable powder (BIT:mancozeb = 1:300) Example 23 3% BIT wettable powder6 15.23 25.42 18.25 80% mancozeb wettable 1194 15.45 12.58 60.12 powderAnticipated control efficacy — — — 67.40 after mixing them 40.2% BIT •mancozeb 1200 16.34  8.90 73.33 wettable powder (BIT:mancozeb = 1:200)Example 24 3% BIT wettable powder 23.5 14.96 21.31 30.23 80% mancozebwettable 1176.5 15.02 15.25 50.25 powder Anticipated control efficacy —— — 65.29 after mixing them 51% BIT • mancozeb 1200 14.22  8.18 71.82wettable powder (BIT:mancozeb = 1:50) CK Water control — 12.34 25.19 —

The test results (in Table 4) show that the control effect of thecombination of BIT and mancozeb on apple ring rot is significantlyimproved, suggesting that the combination of the two components has anobvious synergistic effect in the control of ring rot.

2. Field Efficacy Test of MBIT Combined with Mancozeb

TABLE 5 Control effect of MBIT combined with mancozeb on tomato earlyblight Day 11 after the second application Amount Disease index DiseaseControl No. Agent (a.i.g/ha) before application index effect (%) Example4 5% MBITwater dispersible 28.0 13.45 17.93 29.2 granules 75% mancozebwater 1972.0 12.51 11.03 53.16 dispersible granules Anticipated controlefficacy — — — 66.84 after mixing them 71% BIT • mancozeb 2000.0 15.6771.42 water dispersible granules (MBIT:mancozeb = 1:70) Example 5 3%MBITwater dispersible 19.8 17.35 24.76 24.21 granules 75% mancozeb water1980.2 16.34 13.77 55.23 dispersible granules Anticipated controlefficacy — — — 66.07 after mixing them 50.5% MBIT • mancozeb 2000 14.23 6.51 75.69 water dispersible granules (MBIT:mancozeb = 1:100) Example 63% MBIT water dispersible 8.0 14.36 23.89 11.63 granules 75% mancozebwater 1992.0 16.77 12.59 60.12 dispersible granules Anticipated controlefficacy — — — 64.76 after mixing them 25.1% MBIT • mancozeb 2000 15.28 8.04 72.07 suspension (MBIT:mancozeb = 1:250) Example 14 5% MBITsuspension 500 17.25 10.36 68.09 40% mancozeb suspension 1500 16.3321.15 31.21 Anticipated control efficacy — — — 78.05 after mixing them4% MBIT • mancozeb 2000 18.23  6.49 81.08 suspension (MBIT:mancozeb =1:3) Example 15 5% MBIT suspension 13.2 15.34 23.01 20.33 40% mancozebsuspension 1986.8 14.79 11.64 58.21 Anticipated control efficacy — — —66.71 after mixing them 15.1% MBIT • mancozeb 2000 15.97  7.44 75.25suspension (MBIT:mancozeb = 1:150) Example 16 5% MBIT suspension 95.218.34 19.21 44.35 40% mancozeb suspension 1904.8 10.99 10.72 48.2Anticipated control efficacy — — — 71.17 after mixing them 21% MBIT •mancozeb 2000 14.34  6.64 75.39 suspension (MBIT:mancozeb = 1:20)Example 17 5% MBIT suspension 400.0 16.34 11.31 63.23 40% mancozebsuspension 1600.0 15.27 18.65 35.11 Anticipated control efficacy — — —76.14 after mixing them 5% MBIT • mancozeb 2000 17.45  5.28 83.92suspension (MBIT:mancozeb = 1:4) Example 25 3% MBITwettable powder 6.617.35 29.62 9.31 80% mancozeb wettable 1993.4 15.94 11.71 60.98 powderAnticipated control efficacy — — — 64.61 after mixing them 60.2% MBIT •mancozeb 2000 17.34  9.52 70.84 wettable powder (MBIT:mancozeb = 1:300)Example 26 3% MBITwettable powder 10.0 15.88 26.17 12.46 80% mancozebwettable 1990.0 16.09 12.20 59.74 powder Anticipated control efficacy —— — 64.76 after mixing them 40.2% MBIT • mancozeb 2000 13.45  6.90 72.75wettable powder (MBIT:mancozeb = 1:200) Example 27 3% MBITwettablepowder 39.2 14.78 15.48 44.35 80% mancozeb wettable 1960.8 18.26 20.2141.20 powder Anticipated control efficacy — — — 67.28 after mixing them51% MBIT • mancozeb 2000 15.98  7.71 74.39 wettable powder(MBIT:mancozeb = 1:50) CK Water control — 15.42 29.03 —

The test results (in Table 5) show that the control effect of thecombination of MBIT and mancozeb on tomato early blight is significantlyimproved, suggesting that the combination of the two components has anobvious synergistic effect in the control of tomato early blight.

3. Field Efficacy Test of BBIT Combined with Mancozeb

TABLE 6 Control effect of MBIT combined with mancozeb on pear black spotDay 11 after the second application Amount Disease index Disease ControlNo. Agent (a.i.g/ha) before application index effect (%) Example 7 5%BBIT water dispersible 21 10.35 14.86 28.23 granules 75% mancozeb water1479  9.04  8.27 54.24 dispersible granules Anticipated control efficacy— — — 67.16 after mixing them 71% BBIT • mancozeb 1500 10.98  6.36 71.02water dispersible granules (BBIT:mancozeb = 1:70) Example 8 3% BBITwaterdispersible 14.9 13.2  19.74 25.22 granules 75% mancozeb water 1485.110.4   9.06 56.44 dispersible granules Anticipated control efficacy — —— 67.43 after mixing them 50.5% BBIT • mancozeb 1500  9.99  4.55 77.21water dispersible granules (BBIT:mancozeb = 1:100) Example 9 3%BBITwater dispersible 6.0 11.11 19.53 12.11 granules 75% mancozeb water1494.0 10.89  8.94 58.94 dispersible granules Anticipated controlefficacy — — — 63.91 after mixing them 25.1% BBIT • mancozeb 1500 12.39 6.97 71.88 suspension (BBIT:mancozeb = 1:250) Example 18 5% BBITsuspension 375 15.23 11.44 62.45 40% mancozeb suspension 1125 10.9314.52 33.59 Anticipated control efficacy — — — 75.06 after mixing them4% BBIT • mancozeb 1500 12.32  4.35 82.34 suspension (BBIT:mancozeb =1:3) Example 19 5% BBIT suspension 9.9 10.66 17.10 19.78 40% mancozebsuspension 1490.1 10.99  9.45 57.01 Anticipated control efficacy — — —65.51 after mixing them 15.1% BBIT • mancozeb 1500 15.24  7.66 74.85suspension (BBIT:mancozeb = 1:150) Example 20 5% BBIT suspension 71.415.23 16.71 45.14 40% mancozeb suspension 1428.6  9.78 11.60 40.67Anticipated control efficacy — — — 67.45 after mixing them 21% BBIT •mancozeb 1500 12.45  6.48 73.99 suspension (BBIT:mancozeb = 1:20)Example 21 5% BBIT suspension 300  9.68  9.45 51.21 40% mancozebsuspension 1200 10.64 13.39 37.08 Anticipated control efficacy — — —69.30 after mixing them 5% BBIT • mancozeb 1500 11.23  5.35 76.18suspension (BBIT:mancozeb = 1:4) Example 28 3% BBITwettable powder 5.013.8  24.92 9.72 80% mancozeb wettable 1495.0 15.23 12.26 59.76 powderAnticipated control efficacy — — — 63.67 after mixing them 60.2% BBIT •mancozeb 1500  9.78  5.63 71.20 wettable powder (BBIT:mancozeb = 1:300)Example 29 3% BBITwettable powder 7.5 10.38 17.79 14.32 80% mancozebwettable 1492.5 11.45  9.72 57.57 powder Anticipated control efficacy —— — 63.65 after mixing them 40.2% BBIT • mancozeb 1500  9.78  5.44 72.21wettable powder (BBIT:mancozeb = 1:200) Example 30 3% BBIT wettablepowder 29.4 12.33 14.66 40.56 80% mancozeb wettable 1470.6 10.44 11.4445.21 powder Anticipated control efficacy — — — 67.43 after mixing them51% BBIT • mancozeb 1500 15.01  7.08 76.42 wettable powder(BBIT:mancozeb = 1:50) CK Water control — 11.21 22.42 —

The test results (in Table 5) show that the control effect of thecombination of BBIT and mancozeb on pear black spot is significantlyimproved, suggesting that the combination of the two components has anobvious synergistic effect in the control of pear black spot.

1.-10. (canceled)
 11. A fungicidal composition, consisting of activecomponents A and B, wherein the active component A is1,2-benzisothiazolin-3-one, 2-methyl-1,2-benzisothiazolin-3-one or2-n-butyl-1,2-benzisothiazolin-3-one, and the active component B ismancozeb; and the weight ratio between the two components is 1:3-300,12. The fungicidal composition according to claim 11, wherein the weightratio of the active component A to the active component B is 1:4-280.13. The fungicidal composition according to claim 12, wherein the weightratio of the active component A to the active component B is 1:10-260.14. The fungicidal composition according to claim 11, which is in apesticidally acceptable formulation prepared with the active ingredientsand a pesticide adjuvant or aid.
 15. The fungicidal compositionaccording to claim 14, wherein the mass content of the activeingredients is 2-95%.
 16. The fungicidal composition according to claim14, wherein the formulation is a wettable powder, a suspension, or waterdispersible granules.
 17. The fungicidal composition according to claim14, wherein the pesticide adjuvant or aid is one or more selected from acarrier, a solvent, a dispersant, a wetting agent, a binder, athickener, an adhesive, a surfactant, and a fertilizer.
 18. A methodcomprising controlling crop diseases in an agricultural area by applyingthe fungicidal composition according to claim
 11. 19. The fungicidalcomposition according to claim 12, which is in a pesticidally acceptableformulation prepared with the active ingredients and a pesticideadjuvant or aid.
 20. The fungicidal composition according to claim 13,which is in a pesticidally acceptable formulation prepared with theactive ingredients and a pesticide adjuvant or aid.
 21. The fungicidalcomposition according to claim 19, wherein the mass content of theactive ingredients is 2-95%.
 22. The fungicidal composition according toclaim 19, wherein the formulation is a wettable powder, a suspension, orwater dispersible granules.
 23. The fungicidal composition according toclaim 19, wherein the pesticide adjuvant or aid is one or more selectedfrom a carrier, a solvent, a dispersant, a wetting agent, a binder, athickener, an adhesive, a surfactant, and a fertilizer.
 24. Thefungicidal composition according to claim 20, wherein the mass contentof the active ingredients is 2-95%.
 25. The fungicidal compositionaccording to claim 20, wherein the formulation is a wettable powder, asuspension, or water dispersible granules.
 26. The fungicidalcomposition according to claim 20, wherein the pesticide adjuvant or aidis one or more selected from a carrier, a solvent, a dispersant, awetting agent, a binder, a thickener, an adhesive, a surfactant, and afertilizer.
 27. A method comprising controlling crop diseases in anagricultural area by applying the fungicidal composition according toclaim
 12. 28. A method comprising controlling crop diseases in anagricultural area by applying the fungicidal composition according toclaim 13.